Kinetic Aspects and Heats of Reaction between Components in Thermal Decomposition of Ammonium Nitrate-Calcium (Magnesium) Carbonate Mixtures

The kinetics of heat absorption in thermal decomposition of commercial ammonium nitrate-calcium (magnesium) carbonate mixture and a model mixture of ammonium nitrate and calcium carbonate was studied. Rate equations of the processes and temperature dependences of constants in these equations were determined. The heats of these reactions were calculated.     

Kinetics and Mechanism of Thermal Decomposition of Guanidinium Nitrate and Its Mixtures with Ammonium Nitrate

The kinetics of heat release in thermal decomposition of guanidinium and ammonium nitrates and their mixtures in the liquid phase in a calorimeter was studied. The kinetic equations of these processes and temperature dependences of the kinetic constants in these equations were evaluated. The oxidation rate constants of guanidinium and ammonium cations with molecular nitric acid in aqueous nitric acid solutions were found; these constants were calculated by solution of the reverse problem for salt melts. The temperatures and H values of melting of the initial salts and their eutectic mixture were determined.     

Kinetics of Thermal Decomposition of Solid Propellant Based on Aluminum and Ammonium Perchlorate

Kinetic regularities of the mass loss and heat and-gas release were studied in the thermal decomposition of a solid propellant composed of aluminum, ammonium perchlorate, and a polymer binder. It was shown that, under heating from 40 to 340°C under permanent vacuum conditions, propellant samples decompose without ignition, with the limiting mass loss in the decomposition being 48%. When experiments were performed in air, the propellant formulation decomposes with sharp ignition, with the inflammation temperature (270–287°C) and amount of volatiles released by this instant of time (10–16 wt %) dependent on the heating rate. The kinetic regularities of the mass loss in the decomposition of a solid propellant were described in terms of the polychromatic kinetics model that assumes that the reaction system has ensembles of particles differing in reactivity. The distribution functions of the mass fractions of the propellant by activation energies of decomposition were calculated. The heat release kinetics in the decomposition of a propellant formulation in the temperature range 153–270°C in a closed evacuated system is described by a sum of equations for two parallel reactions: 1st-order reaction with a heat effect Q₁ = 200 ± 5 kJ kg^–1 and 1st-order autocatalysis with heat effect Q₂ = 1900 ± 50 kJ kg–1. The rate constants and the activation parameters of the process were determined.

     

Thermodynamic properties of the ethylammonium nitrate + water system: Partial molar volumes,heat capacities,and expansivities

Partial molar volumes at 15, 25, and 45°C and partial molar heat capacities and expansivities at 25°C for ethylammonium nitrate + water mixtures are reported. The results are compared with those for other aqueous cosolvents, particularly hydrazine and ammonium nitrate.     

Measurement of thermophysical properties of ammonium salts in the solid and molten states

The thermal conductivity, specific heat capacity and thermal diffusivity of solid and molten ammonium thiocyanate, ammonium formate, ammonium acetate and ammonium nitrate were measured in the temperature range 80–190C, including the solid and liquid phases, by using the AC-heated strip (wire) technique. The results indicate that the thermal conductivities depend on the type of the ammonium salt. It was found that the mechanism of heat transfer is due to phonons in the region below the melting points of the salts, while above this region the main mechanism is due to conduction.     

Brønsted acidity of ceric ammonium nitrate in anhydrous DMF. The role of salt and solvent in sucrose cleavage

The generation of an unexpected Brønsted acidity in anhydrous DMF at 50 °C was evidenced by NMR measurements during the investigation on the course of sucrose cleavage by ceric ammonium nitrate (CAN). The formation of a nitrooxy derivative of DMF by reaction with CAN is responsible for this acidity. The reactivity of CAN at 50 °C with several solvents was evaluated by voltammetric and potentiometric measurements. The possible release of protons from these reactions, particularly when aqueous solvent mixtures are used, should always be taken into account in the mechanistic interpretation of CAN synthetic applications.     

Equilibrium and Dynamic Characteristics of Protein Adsorption Layers at Gas-Liquid Interfaces: Theoretical and Experimental Data

Within the framework of a nonideal two-dimensional solution model, equations are derived for the state of a surface layer, adsorption isotherms, and the distribution function of adsorbed protein molecules with respect to their states characterized by different molar surface areas. The derived equations satisfactorily describe the known experimental dependences obtained for equilibrium adsorption layers of some proteins (serum albumin, β-casein, and β-lactoglobulin): the dependences of the surface pressure on concentration and adsorption, the surface layer thickness on adsorption, and the limiting high-frequency elastic modulus of an adsorption layer on the surface pressure. All dependences for a given protein are described by the same set of parameters of the theoretical model. It is shown that the kinetics of protein adsorption studied by dynamic tensiometry, ellipsometry, and the radiotracer technique is consistent with the diffusion model comprising the Ward-Tordai equation and the set of equations describing the equilibrium. The kinetics of protein desorption from the adsorption layer at a liquid-fluid interface is analyzed. The kinetics of β-lactoglobulin desorption is shown to be described by the barrier mechanism.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 4, 2005, pp. 437–449.Original Russian Text Copyright © 2005 by Fainerman, Miller.     

Kinetics and Mechanism of Thermolysis of Mixtures of Ammonium Nitrate with Polynitro Compounds

Kinetics of heat release in thermolysis of mixtures of ammonium nitrate with bis(2,2,2-trinitroethyl) succinate, tetrakis(2,2,2-trinitroethyl) orthocarbonate, technical-grade trinitrotoluene and of the individual polynitro compounds was studied. The temperature dependences of the initial rates of the processes and the time required to attain the maximal rate were determined. A thermolysis mechanism of these mixtures was suggested and the dependence of the thermolysis rate on the properties of the polynitro compounds was accounted for.     

Sequential flow injection analysis of ammonium and nitrate using gas phase molecular absorption spectrometry

A flow injection method on the basis of gas phase molecular absorption is described for the sequential determination of ammonium and nitrate. Two hundred microliters of sample solution is injected into the flow line. For ammonium determination, the sample zone is directed to a line in which reacts with NaOH (13 M) and produces ammonia. But for nitrate determination, the sample zone is passed through the on-line copperized zinc (Zn/Cu) reduction column and produces ammonium ion and in the follows ammonia. The produced ammonia in both cases is purged into the stream of N₂ carrier gas. The gaseous phase is separated from the liquid phase using a gas-liquid separator and then is swept into a flow through cell, which has been positioned in the cell compartment of an UV-Vis spectrophotometer. The absorbance of the gaseous phase is measured at 194 nm. Under selected conditions for sequential analysis of ammonium and nitrate, linear relations were found between the peak heights of absorption signals and concentrations of ammonium (10-650 μg ml⁻¹) and nitrate (20-800 μg ml⁻¹). The limit of detections for ammonium and nitrate analysis were 8 and 10 μg ml⁻¹, respectively. The relative standard deviations of repeated measurements of 50 μg ml⁻¹ of ammonium and nitrate were 2.0, 2.9%, respectively. Maximum sampling rate was about 40 samples/h. The method was applied to the determination of ammonium in pharmaceutical products and the sequential determination of ammonium and nitrate in spiked water samples.     

改性硝酸铵自敏化结构特征

对经复合表面活性剂处理的改性硝酸铵及普通硝酸铵晶体进行电镜扫描,孔径孔容分布,粒径分布,比表面积测定,抗吸湿结块性,差示量热分析以及爆炸性能的实验研究,结果表明,与普通硝酸铵相比,改性硝酸铵的晶形歧化,比表面积大,富含气孔,大部分的有效孔径座落在介孔范围,有较好的粒度级配,晶变热降低,且晶变点后移,具备自敏化结构特征,并且有良好的抗吸湿结块性,用它代替普通硝酸铵所制得的粉状工业炸药具有良好的物理性能和爆炸性能。     

Phosphate release from N ions irradiated 5′-CMP nucleotide and its kinetics

Ion beam irradiation-induced inorganic phosphate (Pi) release from 5′-CMP nucleotide could be divided into two parts: fast process and slow process. The yield of Pi released from the fast process not only had a non-linear response to irradiation dose, but was also influenced by post-irradiation treatments. It was found that heat treatment and alkali treatment increased the yield of Pi but acid treatment decreased it. With the heat treatment lower than 80°C, the Pi release process followed the first order reaction model, but under the conditions of 95°C treatment and alkali treatment the Pi release process followed the second order reaction model. Moreover, the kinetics equations and the rate constants of different models of the Pi release reactions were deduced.     

Theoretical Analysis of Coagulation Kinetics in Brownian Disperse Systems

Analytical solution to the system of differential equations describing the coagulation kinetics in Brownian dilute disperse systems is obtained. The effect of the reversibility of aggregation in the secondary minimum on the coagulation kinetics in the primary minimum is analyzed. It is shown that experimental conditions can substantially affect the theoretical interpretation of experimental data.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 3, 2005, pp. 381–391.Original Russian Text Copyright © 2005 by Mishchuk.     

Hugely enhanced flame retardancy and smoke suppression properties of UHMWPE composites with silicone‐coated expandable graphite

In this paper, silicone‐coated intumescent flame retardants was prepared by an efficient and simple approach, aiming at enhancing the flame‐retardant efficiency and smoke suppression properties. The surface of expandable graphite (EG) was treated prior to the coverage of nonflammable silicone. The resultant silicone‐modified EG hybrid (SEG) was combined with ammonium polyphosphate (APP) and applied as a flame‐retardant and smoke‐suppressant for ultrahigh molecular weight polyethylene (UHMWPE). Compared with UHMWPE/APP/EG (with 15 wt% APP/EG), UHMWPE/APP/SEG (with 15 wt% APP/SEG) gives decrement by 18.5% in the peaks of the heat release rate, 6.33% in total heat release and 13.6% in total smoke release, whereas increment by 23% in tensile strength and 12.1% in elongation at break, respectively. It is suggested that the introduction of silicone on the surface of EG can improve the interfacial compatibility between EG and UHMWPE. Moreover, it can lead to forming more char residue and reducing the release of smoke particulates during combustion process of the composites.     

Temperature resolved X-ray diffraction as a tool of thermal analysis

Time and temperature resolved X-ray diffraction was used for thermal analysis. Series of diffraction patterns were measured, while the samples are heated/cooled stepwise or isothermally with freely selectable temperature programs.The method was applied for the investigation of the phase transitions of ammonium nitrate and HMX (1,3,5,7-tetranitro-1,3,5,7-tetraaza-cyclooctane), when the identification of phases was required. Its capability in the field of kinetics is demonstrated with the isothermal investigation of the solid state reaction of ammonium nitrate with copper oxide and the non-isothermal investigation of the high temperature corrosion of nickel, which was performed by means of a difference procedure. For obtaining structural details peak fitting and Rietveld refinement were applied for the investigation of ammonium nitrate and HMX.We are indebted to Mr. K. O. Hartmann, Mr. H. Fietzek and Mr. H. G. Farr for their assistance during the measurements and for the maintenance of the measuring systems.     

Simultaneous determination of heats,equilibrium and kinetics of adsorption: 1- Ethoxy-2-propanol vapours

The heat, equilibrium, and kinetics of adsorption of 1-ethoxy-2-propanol vapours on granulated activated carbon were determined simultaneously by a reaction calorimeter SETARAM C80 D at T=298.15 K at various relative vapour pressures (0.1< p/p_s<0.8). The adsorption isotherm was correlated by the Freundlich equation. It was observed that the enthalpies of adsorption decrease slightly with increasing of the relative vapour pressure of the adsorptive. The rate of adsorption were calculated from analysis of the heat flux signals and it was found that the mass-transfer coefficient for 1-ethoxy-2-propanol vapours in granulated activated carbon increased with increasing relative vapour pressure of the adsorptive.This revised version was published online in November 2005 with corrections to the Cover Date.     

Study on eruption of heat for Escherichia coli B aroused by lanthanum nitrate and its mechanism

Biological effect of rare-earth lanthanum nitrate on the growth of Escherichia coli B was studied using the calorimetric method. There were exceptional changes on the growth thermogenic curves for high concentrations of lanthanum nitrate. For example, the peak high, the total quantity of heat (Q) of cultures and the growth rate constants (k) are evidently increased when compared with normal E. coli B cultures. When the concentration of lanthanum nitrate was at 300 mg/L and 500 mg/L, and Q of the cultures reached 3.89 and 2.54 times of normal cultures, respectively. The survivability of cells and the biomass of the cultures were measured using biological methods and the results show that the growth and multiplication of cells were inhibited and that the biomass decreased at high concentration of lanthanum nitrate. These revealed that the inhibiting cells discharged more quantity of heat than the normal growing cells. We named this phenomenon as “eruption of heat”. It was suggested that the mechanism for the eruption of heat was that La³⁺ ion damages the outer cell membrane and increases its permeability and the proton-electron potential energy across the cell membrane was reduced or couldn’t even be initiated. Energy could not be translated into ATP effectively in the course of oxidative phosphorylation resulting in heat release. So, the growth of the cells was inhibited due to scarceness of energy ATP. __________ Translated from Acta Chimica Sinica, 2007, 65(10): 917–922 [译自: 化学学报]     

Crystallization kinetics and morphology of poly(butylene succinate‐co‐adipate)

The crystallization kinetics of biodegradable poly(butylene succinate‐co‐adipate) (PBS/A) copolyester was investigated by using differential scanning calorimetry (DSC) and polarized optical microscopy (POM), respectively. The Avrami and Ozawa equations were used to analyze the isothermal and nonisothermal crystallization kinetics, respectively. By using wide‐angle X‐ray diffraction (WAXD), PBS/A was identified to have the same crystal structure with that of PBS. The spherulitic growth rates of PBS/A measured in isothermal conditions are very well comparable with those measured by nonisothermal procedures (cooling rates ranged from 0.5 to 15 °C/min). The kinetic data were examined with the Hoffman–Lauritzen nucleation theory. The observed spherulites of PBS/A with different shapes and textures strongly depend on the crystallization temperatures. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3231–3241, 2005     

Gamma spectrometry for quantification of trace amounts of actinides in concentrated ammonium nitrate solution

A concentrated ammonium nitrate solution (80 g L⁻¹) generated during reprocessing of nuclear fuels was analysed for determining trace amounts of actinides present prior to its reuse or disposal. A gamma spectrometric method using HPGe detector was developed for the assay of uranium (U), plutonium (Pu) and americium (Am) using a suitable calibration sample. The results obtained were validated by liquid scintillation counting. The presence of significant amounts of plutonium necessitated repeated purification of ammonium nitrate before its reuse.     

Isolation and Nitrogen Removal Characteristics of an Aerobic Heterotrophic Nitrifying-Denitrifying Bacterium,Klebsiella sp. TN-10

Nitrogen removal by microorganisms has attracted increasing attention in wastewater treatment. In the present study, a heterotrophic nitrification bacterium was isolated from tannery wastewater and identified as Klebsiella sp. TN-10 based on phenotypic and phylogenetic characteristics. The optimal conditions for cell growth and nitrogen removal were investigated, and the results showed that the greatest ammonium removal rate and maximum biomass were achieved by using sodium pyruvate (7 g/L) as carbon source, C/N 12, pH 7, and temperature 30 °C. Under optimal conditions, the removal rate of ammonia nitrogen reached 96%. Besides, the growth characteristic and the ability of utilizing nitrate and nitrite were investigated. The results demonstrated that strain TN-10 exhibited excellent characteristics to remove both nitrate and nitrite, with the removal rate of 95.44% and 99.87%, respectively. In addition, the nitrite reductase (NiR) and nitrate reductase (NR) involved in denitrification were both active, with the activities of 0.0815 and 0.0283 U/mg proteins, respectively. Furthermore, the aggregation ability, auto-aggregation kinetics, and the relationship between zeta potentials and flocculating efficiency were determined. These results indicated that the strain Klebsiella sp. TN-10, with efficient heterotrophic nitrification-aerobic denitrification ability, has potential application in wastewater treatment.

     

Thermal analysis of high-temperature fast reactions in energetic materials

To get round two main difficulties of the kinetic study of fast reactions of high-temperature decomposition of energetic materials (EM) (spatial non-isothermality and self-inflammation) two new methods for sample preparation called “mechanical dilution” and “thermal dilution” were applied. In the first part of the presentation, some experimental and theoretical data on kinetics of fast high-temperature decomposition of some typical homogeneous and heterogeneous energetic materials (including pyroxylin, ammonia copper chromate, ammonium perchlorate, solid rocket propellants, and others) are given. In a number of cases, kinetic constants of fast reactions dominating at high temperatures were shown to significantly differ from those of low-temperature reactions. The second part of the presentation deals with a new method of thermal analysis—electrothermal analysis (ETA). By using a multi-channel high-speed optical pyrometer, variation of the temperature field in an electrically heated sample of conductive energetic material (or its mixture with metal powder) during its heating followed by thermal explosion is registered. Due to application of this method in the ETA-100 (allowing one to measure kinetic data at the temperature up to 3800 K with a time step as short as 0.1 ms, i.e., for full conversion times as short as 10⁻³ s) some important patterns of mechanisms of gasless combustion and explosion in SHS-mixtures (Si + C, Ni + Al, and Ti + C) were identified. More details regarding these and some additional important aspects can be found in [1, 2].